CA2573047A1 - Method for the production of 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butanitrile - Google Patents
Method for the production of 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butanitrile Download PDFInfo
- Publication number
- CA2573047A1 CA2573047A1 CA002573047A CA2573047A CA2573047A1 CA 2573047 A1 CA2573047 A1 CA 2573047A1 CA 002573047 A CA002573047 A CA 002573047A CA 2573047 A CA2573047 A CA 2573047A CA 2573047 A1 CA2573047 A1 CA 2573047A1
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- Canada
- Prior art keywords
- catalyst
- methylthio
- acrolein
- mmp
- reaction medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 84
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 61
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims description 63
- 239000012429 reaction media Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 claims description 9
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000025 natural resin Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 61
- 230000015572 biosynthetic process Effects 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229930182817 methionine Natural products 0.000 description 4
- 229960004452 methionine Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- HBAHZZVIEFRTEY-UHFFFAOYSA-N 2-heptylcyclohex-2-en-1-one Chemical compound CCCCCCCC1=CCCCC1=O HBAHZZVIEFRTEY-UHFFFAOYSA-N 0.000 description 3
- 229920001367 Merrifield resin Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 1
- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 acetic acid Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- MUQBUKGCVPYANP-UHFFFAOYSA-N formonitrile Chemical compound N#C.N#C MUQBUKGCVPYANP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for the production of 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butanitrile by catalysed addition of methylmercaptan to acrolein and hydrogen cyanide to 3-(methylthio)propanal.
Description
Method for the production of 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butanenitrile The invention relates to a catalytic method for preparing 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butane-nitrile. In particular, the invention describes a process for synthesizing MMP and MMP-cyanohydrin using novel addition catalysts.
Prior art 3-(Methylthio)propanal (MMP)and 2-hydroxy-4-(methylthio)butanenitrile (MMP-cyanohydrin) are intermediates for synthesizing D,L-methionine and the methioninehydroxy analogue 2-hydroxy-4-methylthiobutyric acid (MHA). Methionine is an essential amino acid which inter alia is used as supplement in feedstuffs. MHA is a liquid methionine substitute of lower biological availability.
MMP is prepared by catalytic addition of methylmercaptan (Mc) to acrolein (Ac). Generally, liquid acrolein is reacted with methylmercaptan in a reactor in which liquid MMP and the catalyst are already present in dissolved form (DT 2320544). Also known is the use of gaseous acrolein with methylmercaptan (FR 7520183, FR 7917827, WO 97/00858).
The reaction between methylmercaptan and acrolein can be carried out batchwise or continuously (US 4,225,515, US 5,352,837). As conventional catalysts, use is made of organic bases, e.g. tertiary amines such as hexamethylenetetramine, trialkylamines, e.g. triethyl- or triethanolamine, benzylamines, pyridines, e.g.
2-fluoropyridine and 4-dimethylaminopyridine, picoline, pyrazine, imidazole and nicotinamide, but also copper(II) acetate, mercury methylmercaptide and organic peroxides.
The use of ion exchangers has also been mentioned (FR 7520183). Customarily, the actual addition catalyst is combined with an auxiliary catalyst, an organic acid, e.g.
acetic acid, citric acid or formic acid, or a mineral acid, e.g. sulfuric acid or phosphoric acid, to firstly inhibit the polymerization of acrolein, that is to say the formation of unwanted by-products, and secondly to increase the general yield by conditioning of the added base. The catalyst is not recovered and is lost during the workup.
Typical catalyst concentrations are 0.001 to 0.005 mol%
based on methylmercaptan. The required amount of acid, typically acetic acid, is between 0.5 and 50 mol%. To simplify the MMP preparation method, catalyst and acid can be mixed in a.premix and added as solution. The concentration of catalyst premix in the liquid MMP reaction medium is customarily 0.2 to 0.75 by weight. After the reaction is completed, MMP is separated from the auxiliary and by-products by distillation. During the workup by distillation of the addition product thus prepared, the catalyst premix is lost and, depending on boiling point, must be disposed of via the distillation bottom phase or the off-gas. In principle, portions of the catalyst or of the added acid can pass overhead during the distillation and contaminate the desired pure MMP.
From MMP, by reaction with hydrogen cyanide (prussic acid), with the use of suitable catalysts, the MMP-cyanohydrin 2-hydroxy-4-(methylthio)butanenitrile may be prepared.
Suitable catalysts are abovementioned bases which also catalyze the addition of methylmercaptan to acrolein, e.g.
pyridine or triethylamine. Hydrolysis of MMP-cyanohydrin by e.g. mineral acids produces MHA. Methionine is formed by reaction of MMP-cyanohydrin with ammoniumhydrogencarbonate with formation of hydantoin, which can be saponified by a base, e.g. potassium carbonate or sodium hydroxide. The liberation of methionine occurs with carbon dioxide or sulphuric acid.
Object of the invention It was an object of this invention to provide a catalytic method which makes possible not only the addition of methylmercaptan to acrolein, but also the further reaction of the reaction product to form MMP-cyanohydrin without consuming the catalyst or an additional acid.
Description of the invention The invention is a method for preparing 3-(methylthio)propanal in which a novel catalyst system makes possible the addition of methylmercaptan to acrolein.
In addition, the invention is a method in which this novel catalyst system catalyzes the reaction between MMP and prussic acid for synthesis of MMP-cyanohydrin.
In particular, the invention is a method for continuous preparation of MMP and MMP-cyanohydrin using heterogeneous catalysts which are insoluble in the reaction medium and are therefore not consumed. The addition of auxiliary catalysts such as organic acids, e.g. acetic acid, is not necessary.
The novel catalysts have the general formula (I) A-(CH2)X-N~
(formula I) where R1 and R2 are hydrogen, alkyl having chain lengths between Cl and C12, aryl or heteroaryl. Rl can be different from R2. X is a number between 0 and 6. A is a natural or synthetic resin, e.g. polystyrene. In particular, the polymer-bound bases from the series of the homologous dialkylaminoalkylpolystyrenes and dialkylaminomacro-reticular resins are selected, particularly from dimethylaminoethylpolystyrene, diethylaminoethyl-polystyrene, dimethylaminomethylpolystyrene, diethylaminomethylmacroreticular resins, and especially diethylaminomethylpolystyrene. The said bases are already used in part in other fields of solid-phase chemistry (WO 03/009936, US 4,440,676) and some are commercially available. Furthermore, the synthesis of special derivatives is possible in a simple manner from described resins, e.g. Merrifield resin.
Since the catalysts are soluble neither in the reaction product nor in one of the participating reaction partners, use may be made of any desired amount of catalyst for the reaction which leads to sufficient conversion rates and selectivities. To facilitate the reaction procedure, i.e.
metering of the reaction partners, transport of the starting materials to the active centres of the catalyst and removal of the heat of reaction, a reaction medium should be present in which the catalyst is readily swellable. A resin is readily swellable in a solvent when it can absorb the same as its own mass up to five times its own mass of solvent. The resin increases.its volume here with absorption of the solvent. Preferably, MMP or MMP-cyanohydrin itself can serve as matrix for the reaction.
However, use can also be made of all customary solvents in which the reaction partners, but not the catalyst, are at least partially soluble, e.g. hydrocarbons, halogenated hydrocarbons or ethers. Reactive solvents such as water, alcohols and ketones which, together with the starting materials or the products, can form unwanted by-products are less suitable and may be used only with restrictions.
Based on the active centres, in batch experiments for synthesizing MMP, a molar ratio of catalyst to acrolein of 0.001 to 0.02, preferably 0.001 to 0.01, particularly preferably 0.001 to 0.005 is suitable. In continuous reactions in which the reaction partners and the reaction medium flow continuously past the catalyst, the ratio of acrolein mass to catalyst mass per hour (LHSV value, m/m=h) is between 0.1 and 100, preferably between 1 and 50, particularly preferably between 5 and 50.
The ratio of the reaction medium to acrolein is chosen in batch experiments as between 0.1 and 2. In continuous methods, the ratio of mass flow rate of reaction medium to acrolein should be between 0.5 and 20. To achieve a good conversion of the reactants and for achieving low degradation, the amounts of the starting materials used are controlled such that a slight excess of methylmercapan in the reaction mixture is maintained. The excess should be between 0.01 and 1%, preferably 0.05 and 0.2%, on a molar basis. An excess of acrolein leads to increased formation of high-boiling residues and is therefore not desirable.
When the reaction is carried out, pressure is not a critical factor. It can vary within wide limits. However, since an excessive pressure, by compression of the catalyst bed, can reduce its activity, pressures above 10 bar should be avoided. Preferably, the reaction is to be carried out at atmospheric pressure.
The reaction temperature, depending on pressure and reaction medium, can be selected between -20 and 100 C. At atmospheric pressure and with MMP as matrix, temperatures between 0 and 60 C are suitable, in particular temperatures between 30 and 50 C. Above these temperatures, the selectivity with respect to MMP formation falls, below 0 C, in contrast, the reaction velocity is too low to be able to bring economic advantages.
In the case of batchwise production of MMP, in the reactor ,an initial content of MMP and reaction medium is charged.
The catalyst is suspended in this reaction medium. It is necessary to allow the catalyst to swell in the reaction medium before the start of the reaction, that is to say at the first use, in order to enable the optimum accessibility of the active centres. Then the starting materials methylmercaptan and acrolein are introduced at the same time. The heat of reaction is removed by suitable internals or modifications.
It is advantageous first to charge approximately 10% of the methylmercaptan and only then to continue with introducing acrolein and the remaining methylmercaptan. Methylmercaptan dissolves with reaction heat, forming a hemithioacetal in MMP. In this manner a continuous excess of methylmercaptan is ensured during the reaction. Ari excess of methylmercaptan leads to higher selectivities and thus to minimizing high-boiling by-products. In the event of a sufficient charge of MMP, it is possible to charge all of the methylmercaptan and not add acrolein until after.
After the reaction is completed, the product is filtered off from the catalyst and if appropriate can be further purified. If the reaction product MMP is not soluble in the reaction medium, this MMP can be separated from the reaction medium by phase separation. The catalyst and the reaction medium can be reused in subsequent reactions without further swelling. When MMP is used as reaction medium, it is advantageous to discharge only a portion of the MMP formed and to retain a corresponding operating content together with the catalyst for following charges.
If the crude MMP is to be reacted further to form MMP-cyanohydrin, this is successful simply by adding equimolar amounts of prussic acid to the reaction medium containing invented catalyst. In the batchwise production, for this the complete reaction of the acrolein with methylmercaptan must be completed. Purification of the crude MMP is not necessary.
In continuous production, the prussic acid can be added at a point in the catalyst bed at which the conversion to the MMP is complete. A downstream reaction loop having a separate catalyst bed is also possible. To avoid unnecessary by-products, the reaction should be run with an excess of prussic acid. The molar excess of prussic acid based on MMP should be between 0.01 and 10%, preferably between 0.05 and 1%. The reaction temperature should be between 0 and 100 C, preferably between 20 and 70 C. Either liquefied or gaseous prussic acid can be used.
Brief description of the figures Figure 1 shows a diagrammatic structure of a continuous production of MMP using the inventive heterogeneous solid-phase catalyst in a fixed-bed reactor.
Figure 2 shows a diagrammatic structure of continuous production of MMP using the inventive heterogeneous solid-phase catalyst in a fixed-bed reactor, extended for the reaction of MMP to form MMP-cyanohydrin with prussic acid metering and if appropriate a separate cyanohydrin reaction loop.
In Figure 1 the central apparatus is a fixed-bed reactor having catalyst packing and circulation pump. On the circuit which also comprises a heat exchanger, metering devices for introducing methylmercaptan and acrolein and an ejection for taking off the resultant MMP reaction mixture are present. If the reaction medium is different from MMP, owing to the continuous ejection, a corresponding amount of the solvent taken off must be replenished into the reaction loop. Preferably, the methylmercaptan metering takes place upstream of the acrolein addition. This ensures an excess in time of methylmercaptan at the start of the reaction.
Nevertheless, it can be advantageous, in contrast to the necessary stoichiometry, to add on average a slight excess of methylmercaptan. The excess can be between 0.01 and 1%.
Higher amounts do not lead to further improvement in acrolein yield.
The residence time of the reactants at the catalyst is.
determined via the catalyst volume and flow rate.
Preferably, the ratio of acrolein mass to catalyst mass per hour (LHSV value, m/m=h) is between 0.1 and 100, preferably between 1 and 50, particularly preferably between 5 and 50.
The mass ratio of reaction medium to acrolein should be between 1 and 20. The heat removal at the catalyst is controlled in such a manner that a temperature between 30 and 50 C is achieved. The reaction is operated at atmospheric pressure. Elevated pressures are possible, but do not have an effect on conversion rate.
If the MMP produced is to be further reacted to form MMP-cyanohydrin, the structure is extended by prussic acid metering or if appropriate by a separate cyanohydrin reaction loop as shown in Figure 2.
The inventive method has the advantage of not consuming catalyst or catalyst aid. This is cost-efficient and sustained. In addition, the reaction product MMP or MMP-cyanohydrin is not contaminated by catalysts or catalyst aids. This firstly facilitates the workup of the products and secondly minimizes unwanted side reactions in following stages which are caused by remainders of the catalysts.
The present invention will be described in more detail hereinafter with reference to embodiment examples. These serve only to illustrate the invention and are in no way to be considered limiting in type and scope of these.
Example 1 1.1 Synthesis of dimethylaminomethylpolystyrene resin g (4.5 mmol) of Merrifield resin [CAS 55844-94-5]
(0.9 mmol C1/g), 6.9 g (50 mmol) of triethylamine and 200 ml of dimethylamine solution (400 mmol, 2 M in tetrahydrofuran, THF) are charged into a commercially conventional laboratory autoclave. The mixture is heated at 85 C for a period of 5 hours.
After cooling and depressurising the mixture is filtered off by suction through a glass frit and the filter cake is washed first chloride-free with water, and then rewashed with 200 ml of THF. The resin dried at 60 C can, after swelling, be used directly in the following experiments.
This produces 4.8 g of product which consists according to NMR of >90% of the dimethylbenzylamine-functionalized resin. In addition to unreacted benzyl chloride, benzyl alcohol is a minor functionality.
1.2 Batchwise synthesis of 3-(methylthio)propanal In a reaction flask having dropping funnel and gas introduction, 0.5 g of dimethylaminomethylpolystyrene resin (activity approximately 18 mmol/l MMP) are dispersed in 25 ml of distilled pure MMP as charge. The resin is allowed to swell for 1 h. At 0 C, in the course of 10 min, 10 g (208 mmol) of methylmercaptan are then passed in, which immediately dissolves with formation of an MMP-hemimercaptal. After introduction is completed, 11.5 g (205 mmol) of acrolein are added dropwise and further stirred at 0 C. After two hours, the catalyst is filtered off and the MMP analyzed. This produces an acrolein conversion rate of 98% and a yield of 95%. The residue in the bottom phase on distillation of the crude MMP is 0.19%.
The catalyst filtered off can be used directly in following experiments without further swelling. Use for ten times shows no loss of activity.
1.3 Batchwise synthesis of 2-hydroxy-4-(methylthio)-butanenitrile For the further reaction with prussic acid, the catalyst is not filtered off, but prussic acid (12.6 g, 466 mmol, 1.05 equivalent) is added dropwise to the MMP reaction mixture with cooling at approximately 35 C in the course of 30 min. After reaction is completed, the mixture is filtered off from the catalyst. This produces 62 g of MMP-cyanohydrin of a purity of >98%. The repeated reuse of the catalyst leads to no loss of activity.
1.4 Continuous synthesis of 3-(methylthio)propanal 4 mmol of dimethylaminomethylpolystyrene resin (equivalent to 4.4 g dry) previously swollen in MMP are packed into a reaction tube. The tubular reactor is connected into a circulation loop charged with pure MMP with a pump. The capacity in the loop is approximately 5 ml. A further pump permits the introduction of acrolein upstream of the reaction tube. In addition, a valve makes it possible to introduce liquid or gaseous methylmercaptan into the stream. An accompanying heat exchanger serves for heating the reaction loop to 50 C. To start the reaction 0.25 g of acrolein/min and 0.21 g of methylmercaptan/min are added.
The volume fed to the reaction loop is removed at atmospheric pressure at a discharge point. The volumetric ratio of feed to circuit is 1/5. The reaction is in the steady state after approximately 30 min. Analysis of a representative crude MMP sample shows acrolein conversion rates > 99% and MMP purities of approximately 93%.
The amount of MMP taken off from the reaction loop is reacted in a second reaction loop to give MMP-cyanohydrin.
The set-up and procedure correspond to the above description for the reaction of acrolein with methylmercaptan. The amount of catalyst is 4 mmol, and the feed rate of HCN is 0.12 g/min. The volume fed to the reaction loop is taken off at atmospheric pressure at a discharge point. The volumetric ratio of feed to circuit is 1/5, and the temperature is maintained at 40 C. The reaction is in the steady state after approximately 30 min.
Analysis of a representative MMP-cyanohydrin sample shows MMP conversion rates > 99% and purities of approximately 92%.
Example 2 2.1 Synthesis of diethylaminomethylpolystyrene resin In a stirred flask having a reflux condenser, 30 g (27 mmol) of Merrifield resin [CAS 55844-94-5] (0.9 mmol C1/g), 30.4 g (300 mmol) of triethylamine and 87.8 g (1.20 mol) of diethylamine are suspended in 420 ml of methyl isobutyl ketone. The mixture is kept at reflux for 6 hours. After it has cooled to room temperature it is filtered off by suction through a glass frit and the filtercake is washed chloride-free with water. The resin dried at 60 C can, after swelling, be used directly in following experiments. This produces 32 g of product of which, according to NMR, >90% consists of the diethylbenzylamino-functionalized resin. In addition to unreacted benzyl chloride, benzyl alcohol is a minor functionality.
2.2 Batchwise synthesis of 3-(methylthio)propanal Corresponding to the procedure of Example 1, 0.5 g of diethylaminomethylpolystyrene resin are reacted with acrolein and methylmercaptan.
After 2 hours this produces an acrolein conversion rate of >99% and a yield of >96%. The residue in the bottom phase in distillation of the crude MMP is 0.15%.
The further reaction to form MMP-cyanohydrin delivers this at conversion rates >99% at a purity of >95%.
The catalyst filtered off can be used directly without further swelling in the following experiments. Use for ten.
times shows no loss of activity.
2.3 Continuous synthesis of 3-(methylthio)propanal Corresponding to the procedure from Example 1, 4.4 g (approximately 4 mmol) of diethylaminomethylpolystyrene resins are reacted with acrolein and methylmercaptan.
Analysis of a representative crude MMP sample shows acrolein conversion rates > 99% and MMP purities of approximately 94%, while analysis of a representative MMP-cyanohydrin sample after addition of prussic acid shows MMP
conversion"rates > 9926 and purities of approximately 93%.
Explanations to the figures:
(1) Input of acrolein (2) Catalyst (3) Heat exchanger (4) Circulation pump (5) Discharge of MMP
Prior art 3-(Methylthio)propanal (MMP)and 2-hydroxy-4-(methylthio)butanenitrile (MMP-cyanohydrin) are intermediates for synthesizing D,L-methionine and the methioninehydroxy analogue 2-hydroxy-4-methylthiobutyric acid (MHA). Methionine is an essential amino acid which inter alia is used as supplement in feedstuffs. MHA is a liquid methionine substitute of lower biological availability.
MMP is prepared by catalytic addition of methylmercaptan (Mc) to acrolein (Ac). Generally, liquid acrolein is reacted with methylmercaptan in a reactor in which liquid MMP and the catalyst are already present in dissolved form (DT 2320544). Also known is the use of gaseous acrolein with methylmercaptan (FR 7520183, FR 7917827, WO 97/00858).
The reaction between methylmercaptan and acrolein can be carried out batchwise or continuously (US 4,225,515, US 5,352,837). As conventional catalysts, use is made of organic bases, e.g. tertiary amines such as hexamethylenetetramine, trialkylamines, e.g. triethyl- or triethanolamine, benzylamines, pyridines, e.g.
2-fluoropyridine and 4-dimethylaminopyridine, picoline, pyrazine, imidazole and nicotinamide, but also copper(II) acetate, mercury methylmercaptide and organic peroxides.
The use of ion exchangers has also been mentioned (FR 7520183). Customarily, the actual addition catalyst is combined with an auxiliary catalyst, an organic acid, e.g.
acetic acid, citric acid or formic acid, or a mineral acid, e.g. sulfuric acid or phosphoric acid, to firstly inhibit the polymerization of acrolein, that is to say the formation of unwanted by-products, and secondly to increase the general yield by conditioning of the added base. The catalyst is not recovered and is lost during the workup.
Typical catalyst concentrations are 0.001 to 0.005 mol%
based on methylmercaptan. The required amount of acid, typically acetic acid, is between 0.5 and 50 mol%. To simplify the MMP preparation method, catalyst and acid can be mixed in a.premix and added as solution. The concentration of catalyst premix in the liquid MMP reaction medium is customarily 0.2 to 0.75 by weight. After the reaction is completed, MMP is separated from the auxiliary and by-products by distillation. During the workup by distillation of the addition product thus prepared, the catalyst premix is lost and, depending on boiling point, must be disposed of via the distillation bottom phase or the off-gas. In principle, portions of the catalyst or of the added acid can pass overhead during the distillation and contaminate the desired pure MMP.
From MMP, by reaction with hydrogen cyanide (prussic acid), with the use of suitable catalysts, the MMP-cyanohydrin 2-hydroxy-4-(methylthio)butanenitrile may be prepared.
Suitable catalysts are abovementioned bases which also catalyze the addition of methylmercaptan to acrolein, e.g.
pyridine or triethylamine. Hydrolysis of MMP-cyanohydrin by e.g. mineral acids produces MHA. Methionine is formed by reaction of MMP-cyanohydrin with ammoniumhydrogencarbonate with formation of hydantoin, which can be saponified by a base, e.g. potassium carbonate or sodium hydroxide. The liberation of methionine occurs with carbon dioxide or sulphuric acid.
Object of the invention It was an object of this invention to provide a catalytic method which makes possible not only the addition of methylmercaptan to acrolein, but also the further reaction of the reaction product to form MMP-cyanohydrin without consuming the catalyst or an additional acid.
Description of the invention The invention is a method for preparing 3-(methylthio)propanal in which a novel catalyst system makes possible the addition of methylmercaptan to acrolein.
In addition, the invention is a method in which this novel catalyst system catalyzes the reaction between MMP and prussic acid for synthesis of MMP-cyanohydrin.
In particular, the invention is a method for continuous preparation of MMP and MMP-cyanohydrin using heterogeneous catalysts which are insoluble in the reaction medium and are therefore not consumed. The addition of auxiliary catalysts such as organic acids, e.g. acetic acid, is not necessary.
The novel catalysts have the general formula (I) A-(CH2)X-N~
(formula I) where R1 and R2 are hydrogen, alkyl having chain lengths between Cl and C12, aryl or heteroaryl. Rl can be different from R2. X is a number between 0 and 6. A is a natural or synthetic resin, e.g. polystyrene. In particular, the polymer-bound bases from the series of the homologous dialkylaminoalkylpolystyrenes and dialkylaminomacro-reticular resins are selected, particularly from dimethylaminoethylpolystyrene, diethylaminoethyl-polystyrene, dimethylaminomethylpolystyrene, diethylaminomethylmacroreticular resins, and especially diethylaminomethylpolystyrene. The said bases are already used in part in other fields of solid-phase chemistry (WO 03/009936, US 4,440,676) and some are commercially available. Furthermore, the synthesis of special derivatives is possible in a simple manner from described resins, e.g. Merrifield resin.
Since the catalysts are soluble neither in the reaction product nor in one of the participating reaction partners, use may be made of any desired amount of catalyst for the reaction which leads to sufficient conversion rates and selectivities. To facilitate the reaction procedure, i.e.
metering of the reaction partners, transport of the starting materials to the active centres of the catalyst and removal of the heat of reaction, a reaction medium should be present in which the catalyst is readily swellable. A resin is readily swellable in a solvent when it can absorb the same as its own mass up to five times its own mass of solvent. The resin increases.its volume here with absorption of the solvent. Preferably, MMP or MMP-cyanohydrin itself can serve as matrix for the reaction.
However, use can also be made of all customary solvents in which the reaction partners, but not the catalyst, are at least partially soluble, e.g. hydrocarbons, halogenated hydrocarbons or ethers. Reactive solvents such as water, alcohols and ketones which, together with the starting materials or the products, can form unwanted by-products are less suitable and may be used only with restrictions.
Based on the active centres, in batch experiments for synthesizing MMP, a molar ratio of catalyst to acrolein of 0.001 to 0.02, preferably 0.001 to 0.01, particularly preferably 0.001 to 0.005 is suitable. In continuous reactions in which the reaction partners and the reaction medium flow continuously past the catalyst, the ratio of acrolein mass to catalyst mass per hour (LHSV value, m/m=h) is between 0.1 and 100, preferably between 1 and 50, particularly preferably between 5 and 50.
The ratio of the reaction medium to acrolein is chosen in batch experiments as between 0.1 and 2. In continuous methods, the ratio of mass flow rate of reaction medium to acrolein should be between 0.5 and 20. To achieve a good conversion of the reactants and for achieving low degradation, the amounts of the starting materials used are controlled such that a slight excess of methylmercapan in the reaction mixture is maintained. The excess should be between 0.01 and 1%, preferably 0.05 and 0.2%, on a molar basis. An excess of acrolein leads to increased formation of high-boiling residues and is therefore not desirable.
When the reaction is carried out, pressure is not a critical factor. It can vary within wide limits. However, since an excessive pressure, by compression of the catalyst bed, can reduce its activity, pressures above 10 bar should be avoided. Preferably, the reaction is to be carried out at atmospheric pressure.
The reaction temperature, depending on pressure and reaction medium, can be selected between -20 and 100 C. At atmospheric pressure and with MMP as matrix, temperatures between 0 and 60 C are suitable, in particular temperatures between 30 and 50 C. Above these temperatures, the selectivity with respect to MMP formation falls, below 0 C, in contrast, the reaction velocity is too low to be able to bring economic advantages.
In the case of batchwise production of MMP, in the reactor ,an initial content of MMP and reaction medium is charged.
The catalyst is suspended in this reaction medium. It is necessary to allow the catalyst to swell in the reaction medium before the start of the reaction, that is to say at the first use, in order to enable the optimum accessibility of the active centres. Then the starting materials methylmercaptan and acrolein are introduced at the same time. The heat of reaction is removed by suitable internals or modifications.
It is advantageous first to charge approximately 10% of the methylmercaptan and only then to continue with introducing acrolein and the remaining methylmercaptan. Methylmercaptan dissolves with reaction heat, forming a hemithioacetal in MMP. In this manner a continuous excess of methylmercaptan is ensured during the reaction. Ari excess of methylmercaptan leads to higher selectivities and thus to minimizing high-boiling by-products. In the event of a sufficient charge of MMP, it is possible to charge all of the methylmercaptan and not add acrolein until after.
After the reaction is completed, the product is filtered off from the catalyst and if appropriate can be further purified. If the reaction product MMP is not soluble in the reaction medium, this MMP can be separated from the reaction medium by phase separation. The catalyst and the reaction medium can be reused in subsequent reactions without further swelling. When MMP is used as reaction medium, it is advantageous to discharge only a portion of the MMP formed and to retain a corresponding operating content together with the catalyst for following charges.
If the crude MMP is to be reacted further to form MMP-cyanohydrin, this is successful simply by adding equimolar amounts of prussic acid to the reaction medium containing invented catalyst. In the batchwise production, for this the complete reaction of the acrolein with methylmercaptan must be completed. Purification of the crude MMP is not necessary.
In continuous production, the prussic acid can be added at a point in the catalyst bed at which the conversion to the MMP is complete. A downstream reaction loop having a separate catalyst bed is also possible. To avoid unnecessary by-products, the reaction should be run with an excess of prussic acid. The molar excess of prussic acid based on MMP should be between 0.01 and 10%, preferably between 0.05 and 1%. The reaction temperature should be between 0 and 100 C, preferably between 20 and 70 C. Either liquefied or gaseous prussic acid can be used.
Brief description of the figures Figure 1 shows a diagrammatic structure of a continuous production of MMP using the inventive heterogeneous solid-phase catalyst in a fixed-bed reactor.
Figure 2 shows a diagrammatic structure of continuous production of MMP using the inventive heterogeneous solid-phase catalyst in a fixed-bed reactor, extended for the reaction of MMP to form MMP-cyanohydrin with prussic acid metering and if appropriate a separate cyanohydrin reaction loop.
In Figure 1 the central apparatus is a fixed-bed reactor having catalyst packing and circulation pump. On the circuit which also comprises a heat exchanger, metering devices for introducing methylmercaptan and acrolein and an ejection for taking off the resultant MMP reaction mixture are present. If the reaction medium is different from MMP, owing to the continuous ejection, a corresponding amount of the solvent taken off must be replenished into the reaction loop. Preferably, the methylmercaptan metering takes place upstream of the acrolein addition. This ensures an excess in time of methylmercaptan at the start of the reaction.
Nevertheless, it can be advantageous, in contrast to the necessary stoichiometry, to add on average a slight excess of methylmercaptan. The excess can be between 0.01 and 1%.
Higher amounts do not lead to further improvement in acrolein yield.
The residence time of the reactants at the catalyst is.
determined via the catalyst volume and flow rate.
Preferably, the ratio of acrolein mass to catalyst mass per hour (LHSV value, m/m=h) is between 0.1 and 100, preferably between 1 and 50, particularly preferably between 5 and 50.
The mass ratio of reaction medium to acrolein should be between 1 and 20. The heat removal at the catalyst is controlled in such a manner that a temperature between 30 and 50 C is achieved. The reaction is operated at atmospheric pressure. Elevated pressures are possible, but do not have an effect on conversion rate.
If the MMP produced is to be further reacted to form MMP-cyanohydrin, the structure is extended by prussic acid metering or if appropriate by a separate cyanohydrin reaction loop as shown in Figure 2.
The inventive method has the advantage of not consuming catalyst or catalyst aid. This is cost-efficient and sustained. In addition, the reaction product MMP or MMP-cyanohydrin is not contaminated by catalysts or catalyst aids. This firstly facilitates the workup of the products and secondly minimizes unwanted side reactions in following stages which are caused by remainders of the catalysts.
The present invention will be described in more detail hereinafter with reference to embodiment examples. These serve only to illustrate the invention and are in no way to be considered limiting in type and scope of these.
Example 1 1.1 Synthesis of dimethylaminomethylpolystyrene resin g (4.5 mmol) of Merrifield resin [CAS 55844-94-5]
(0.9 mmol C1/g), 6.9 g (50 mmol) of triethylamine and 200 ml of dimethylamine solution (400 mmol, 2 M in tetrahydrofuran, THF) are charged into a commercially conventional laboratory autoclave. The mixture is heated at 85 C for a period of 5 hours.
After cooling and depressurising the mixture is filtered off by suction through a glass frit and the filter cake is washed first chloride-free with water, and then rewashed with 200 ml of THF. The resin dried at 60 C can, after swelling, be used directly in the following experiments.
This produces 4.8 g of product which consists according to NMR of >90% of the dimethylbenzylamine-functionalized resin. In addition to unreacted benzyl chloride, benzyl alcohol is a minor functionality.
1.2 Batchwise synthesis of 3-(methylthio)propanal In a reaction flask having dropping funnel and gas introduction, 0.5 g of dimethylaminomethylpolystyrene resin (activity approximately 18 mmol/l MMP) are dispersed in 25 ml of distilled pure MMP as charge. The resin is allowed to swell for 1 h. At 0 C, in the course of 10 min, 10 g (208 mmol) of methylmercaptan are then passed in, which immediately dissolves with formation of an MMP-hemimercaptal. After introduction is completed, 11.5 g (205 mmol) of acrolein are added dropwise and further stirred at 0 C. After two hours, the catalyst is filtered off and the MMP analyzed. This produces an acrolein conversion rate of 98% and a yield of 95%. The residue in the bottom phase on distillation of the crude MMP is 0.19%.
The catalyst filtered off can be used directly in following experiments without further swelling. Use for ten times shows no loss of activity.
1.3 Batchwise synthesis of 2-hydroxy-4-(methylthio)-butanenitrile For the further reaction with prussic acid, the catalyst is not filtered off, but prussic acid (12.6 g, 466 mmol, 1.05 equivalent) is added dropwise to the MMP reaction mixture with cooling at approximately 35 C in the course of 30 min. After reaction is completed, the mixture is filtered off from the catalyst. This produces 62 g of MMP-cyanohydrin of a purity of >98%. The repeated reuse of the catalyst leads to no loss of activity.
1.4 Continuous synthesis of 3-(methylthio)propanal 4 mmol of dimethylaminomethylpolystyrene resin (equivalent to 4.4 g dry) previously swollen in MMP are packed into a reaction tube. The tubular reactor is connected into a circulation loop charged with pure MMP with a pump. The capacity in the loop is approximately 5 ml. A further pump permits the introduction of acrolein upstream of the reaction tube. In addition, a valve makes it possible to introduce liquid or gaseous methylmercaptan into the stream. An accompanying heat exchanger serves for heating the reaction loop to 50 C. To start the reaction 0.25 g of acrolein/min and 0.21 g of methylmercaptan/min are added.
The volume fed to the reaction loop is removed at atmospheric pressure at a discharge point. The volumetric ratio of feed to circuit is 1/5. The reaction is in the steady state after approximately 30 min. Analysis of a representative crude MMP sample shows acrolein conversion rates > 99% and MMP purities of approximately 93%.
The amount of MMP taken off from the reaction loop is reacted in a second reaction loop to give MMP-cyanohydrin.
The set-up and procedure correspond to the above description for the reaction of acrolein with methylmercaptan. The amount of catalyst is 4 mmol, and the feed rate of HCN is 0.12 g/min. The volume fed to the reaction loop is taken off at atmospheric pressure at a discharge point. The volumetric ratio of feed to circuit is 1/5, and the temperature is maintained at 40 C. The reaction is in the steady state after approximately 30 min.
Analysis of a representative MMP-cyanohydrin sample shows MMP conversion rates > 99% and purities of approximately 92%.
Example 2 2.1 Synthesis of diethylaminomethylpolystyrene resin In a stirred flask having a reflux condenser, 30 g (27 mmol) of Merrifield resin [CAS 55844-94-5] (0.9 mmol C1/g), 30.4 g (300 mmol) of triethylamine and 87.8 g (1.20 mol) of diethylamine are suspended in 420 ml of methyl isobutyl ketone. The mixture is kept at reflux for 6 hours. After it has cooled to room temperature it is filtered off by suction through a glass frit and the filtercake is washed chloride-free with water. The resin dried at 60 C can, after swelling, be used directly in following experiments. This produces 32 g of product of which, according to NMR, >90% consists of the diethylbenzylamino-functionalized resin. In addition to unreacted benzyl chloride, benzyl alcohol is a minor functionality.
2.2 Batchwise synthesis of 3-(methylthio)propanal Corresponding to the procedure of Example 1, 0.5 g of diethylaminomethylpolystyrene resin are reacted with acrolein and methylmercaptan.
After 2 hours this produces an acrolein conversion rate of >99% and a yield of >96%. The residue in the bottom phase in distillation of the crude MMP is 0.15%.
The further reaction to form MMP-cyanohydrin delivers this at conversion rates >99% at a purity of >95%.
The catalyst filtered off can be used directly without further swelling in the following experiments. Use for ten.
times shows no loss of activity.
2.3 Continuous synthesis of 3-(methylthio)propanal Corresponding to the procedure from Example 1, 4.4 g (approximately 4 mmol) of diethylaminomethylpolystyrene resins are reacted with acrolein and methylmercaptan.
Analysis of a representative crude MMP sample shows acrolein conversion rates > 99% and MMP purities of approximately 94%, while analysis of a representative MMP-cyanohydrin sample after addition of prussic acid shows MMP
conversion"rates > 9926 and purities of approximately 93%.
Explanations to the figures:
(1) Input of acrolein (2) Catalyst (3) Heat exchanger (4) Circulation pump (5) Discharge of MMP
(6) Input of methylmercaptan (7) Input of prussic acid (8) Discharge of MMP-cyanohydrin
Claims (31)
1. Method for preparing 3-(methylthio)propanal by addition of methylmercaptan to acrolein in the presence of a) a heterogeneous catalyst, and b) a reaction medium, characterized in that the heterogeneous catalyst is not soluble in the reaction medium.
2. Method according to Claim 1, characterized in that the heterogeneous catalyst has the general formula where R1 and R2 are hydrogen, alkyl having chain lengths between C1 and C12, aryl or heteroaryl;
R1 can be different from R2;
X is a number between 0 and 6; and A is a natural or synthetic resin.
R1 can be different from R2;
X is a number between 0 and 6; and A is a natural or synthetic resin.
3. Method according to Claim 2, characterized in that A
in the formula I is a polystyrene.
in the formula I is a polystyrene.
4. Method according to Claim 2, characterized in that the catalyst according to formula I is a polymer-bound base selected from the group consisting of the homologous dialkylaminoalkylpolystyrenes or dialkylaminomacroreticular resins.
5. Method according to Claim 4, characterized in that the catalyst according to formula I is diethylaminoethylpolystyrene, diethylaminomethylpolystyrene, dimethylaminomethylpolystyrene, diethylaminomethylmacroreticular resin or dimethylaminoethylpolystyrene.
6. Method according to Claim 1, characterized in that the reaction medium is a hydrocarbon, a halogenated hydrocarbon, an ether, 3-(methylthio)propanal or 2-hydroxy-4-(methylthio)butanenitrile.
7. Method according to Claim 6, characterized in that the reaction medium is 3-(methylthio)propanal.
8. Method according to Claim 1, characterized in that it is carried out at temperatures of -20°C to 100°C.
9. Method according to Claim 8, characterized in that the temperature is between 0°C and 60°C.
10. Method according to Claim 8 or 9, characterized in that the temperature is between 30°C and 50°C.
11. Method according to Claim 1, characterized in that, based on the active centres, the molar ratio of catalyst to acrolein is from 0.001 to 0.02.
12. Method according to Claim 11, characterized in that the molar ratio of catalyst to acrolein is from 0.001 to 0.01.
13. Method according to Claim 12, characterized in that the molar ratio of catalyst to acrolein is from 0.001 to 0.005.
14. Method according to Claim 1, characterized in that the molar excess of methylmercaptan based on acrolein is between 0.01 and 1%, preferably between 0.05 and 0.2%.
15. Method according to Claim 1, characterized in that the method is a batch method.
16 16. Method according to Claim 15, characterized in that the ratio of reaction medium to acrolein is between 0.1 and 2.
17. Method according to Claim 1, characterized in that the method is continuous.
18. Method according to Claim 17, characterized in that the ratio of flow rates by mass of reaction medium to acrolein is between 0.5 and 20.
19. Method for preparing 2-hydroxy-4-(methylthio)butanenitrile by addition of prussic acid to 3-(methylthio)propanal in the presence of a) a heterogeneous catalyst, and b) a reaction medium, characterized in that the heterogeneous catalyst is not soluble in the reaction medium.
20. Method according to Claim 19, characterized in that the heterogeneous catalyst has the general formula where R1 and R2 are hydrogen, alkyl having chain lengths between C1 and C12, aryl or heteroaryl;
R1 can be different from R2 X is a number between 0 and 6, and A is a natural or synthetic resin.
R1 can be different from R2 X is a number between 0 and 6, and A is a natural or synthetic resin.
21. Method according to Claim 20, characterized in that A
in the formula I is a polystyrene.
in the formula I is a polystyrene.
22. Method according to Claim 20, characterized in that the catalyst according to formula I is a polymer-bound base selected from the group consisting of the homologous dialkylaminoalkylpolystyrenes or dialkylaminomacroreticular resins.
23. Method according to Claim 22, characterized in that the catalyst according to formula I is diethylaminoethylpolystyrene, diethylaminomethylpolystyrene, dimethylaminomethylpolystyrene, diethylaminomethylmacroreticular resin or dimethylaminoethylpolystyrene.
24. Method according to Claim 19, characterized in that the reaction medium is a hydrocarbon, a halogenated hydrocarbon, an ether, or 2-hydroxy-4-(methylthio)butanenitrile.
25. Method according to Claim 24, characterized in that the reaction medium is 2-hydroxy-4-(methylthio)-butanenitrile.
26. Method according to Claim 19, characterized in that it is carried out at temperatures of 0°C to 100°C.
27. Method according to Claim 26, characterized in that the temperature is between 20°C and 70°C.
28. Method according to Claim 19, characterized in that the ratio of catalyst to 3-(methylthio)propanal is between 0.001 and 0.02.
29. Method according to Claim 19, characterized in that the molar excess of prussic acid to 3-(methylthio)propanal is between 0.01 and 10%, preferably between 0.05 and 1%.
30. Method according to Claim 19, characterized in that the method is a batch method.
31. Method according to Claim 19, characterized in that the method is continuous.
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PCT/EP2005/007666 WO2006015684A2 (en) | 2004-08-05 | 2005-07-14 | Method for the production of 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butanitrile |
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DE102005003990A1 (en) * | 2005-01-28 | 2006-08-03 | Degussa Ag | Preparation of 3-(alkylthio)propanal comprises reaction of glycerin or compounds obtained from glycerin, with a sulfur compound or compounds obtained from sulfur compound in the presence of a catalyst |
JP5182198B2 (en) * | 2009-04-06 | 2013-04-10 | 住友化学株式会社 | Method for producing 3-methylthiopropanal |
JP5402864B2 (en) * | 2010-07-20 | 2014-01-29 | 住友化学株式会社 | Method for producing 3-methylthiopropanal |
FR2966456B1 (en) * | 2010-10-26 | 2013-03-15 | Adisseo France Sas | PROCESS FOR OBTAINING ACROLEIN BY CATALYTIC DEHYDRATION OF GLYCEROL OR GLYCERIN |
EP2468383A1 (en) * | 2010-12-22 | 2012-06-27 | Evonik Degussa GmbH | Method for thermal post-combustion of waste gases from the production of acrylic acid and prussic acid |
JP5930330B2 (en) | 2011-02-23 | 2016-06-08 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | Storage-stable 2-hydroxy-4- (methylthio) butyronitrile |
MX341595B (en) | 2011-02-23 | 2016-08-26 | Evonik Degussa Gmbh | Method for producing 2-hydroxy-4-(methylthio)butanenitrile from 3-(methylthio)propanal and hydrogen cyanide. |
CN105452210B (en) | 2013-06-03 | 2018-11-20 | 赢创德固赛有限公司 | The method for preparing methacrylaldehyde |
CN107417570B (en) * | 2017-09-14 | 2020-04-14 | 哈尔滨理工大学 | Method for preparing α -hydroxynitrile by using acetone cyanohydrin |
CN111116437B (en) | 2018-11-01 | 2021-02-05 | 山东新和成氨基酸有限公司 | Method and apparatus for producing 2-hydroxy-4-methylthiobutyric acid and intermediate thereof |
CN109651215B (en) * | 2019-02-14 | 2023-12-22 | 天宝动物营养科技股份有限公司 | Continuous preparation process and device of 2-hydroxy-4-methylthiobutyronitrile |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2542768A (en) * | 1945-10-24 | 1951-02-20 | Du Pont | Hydroxy-methylmercaptobutyronitrile |
DE2320544C2 (en) * | 1973-04-21 | 1975-06-05 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of 3-methyl mercaptopropionaldehyde |
FR2314917A1 (en) | 1975-06-20 | 1977-01-14 | Rhone Poulenc Ind | MANUFACTURING PROCESS OF BETA-METHYLTHIOPROPIONIC ALDEHYDE |
DE2623285C3 (en) | 1976-05-25 | 1980-10-02 | Gebrueder Grau Und Co Kg Chem. Fabrik, 7070 Schwaebisch Gmuend | Fragrance composition |
FR2460925A1 (en) * | 1979-07-10 | 1981-01-30 | Rhone Poulenc Ind | PROCESS FOR THE DIRECT PREPARATION OF BETA-METHYLTHIOPROPIONIC ALDEHYDE |
FR2480925A1 (en) | 1980-04-22 | 1981-10-23 | Electricite De France | Heat exchanger, esp. for nuclear reactors - where one fluid flows through tube modules which can be isolated by valves or easily replaced |
US4440676A (en) | 1981-12-24 | 1984-04-03 | The British Petroleum Company P.L.C. | Process for the production of a dipeptide, a polypeptide or a protein |
JP3219544B2 (en) * | 1992-05-21 | 2001-10-15 | ダイセル化学工業株式会社 | Method for producing 2-hydroxy-4-methylthiobutanoic acid |
US5905171A (en) | 1995-06-22 | 1999-05-18 | Novus International, Inc. | Process for the preparation of 3-(methylthio)propanal |
US5352837A (en) | 1993-06-08 | 1994-10-04 | Novus International, Inc. | Process for the preparation of 3-(methylthio)propanal |
US5663409A (en) * | 1995-06-07 | 1997-09-02 | Novus International, Inc. | Process for the preparation of 3-(methylthio) propanal and 2-hydroxy-4-(methylthio) butanenitrile |
AR002174A1 (en) * | 1995-06-07 | 1998-01-07 | Novus Int Inc | PROCESS FOR THE PREPARATION OF 3- (METHYLTI) PROPANAL AND 2-HYDROXY-4-METHYL) BUTANONITRILE |
ATE240924T1 (en) * | 1996-04-01 | 2003-06-15 | Union Carbide Chem Plastic | METHOD FOR PRODUCING METHYL MERCATOPROPANAL |
JP4517486B2 (en) * | 2000-09-25 | 2010-08-04 | 住友化学株式会社 | Process for producing 2-hydroxy-4-methylthiobutanenitrile |
EP1409131A2 (en) * | 2001-07-23 | 2004-04-21 | Andrew Bruce Holmes | Palladium-catalysed carbon-carbon bond forming reactions in compressed carbon dioxide |
JP4186572B2 (en) * | 2002-09-27 | 2008-11-26 | 住友化学株式会社 | Method for producing 3-methylthiopropanal |
-
2004
- 2004-08-05 DE DE102004038053A patent/DE102004038053A1/en not_active Ceased
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2005
- 2005-07-14 RU RU2007108071/04A patent/RU2383531C2/en not_active IP Right Cessation
- 2005-07-14 ES ES05775924.3T patent/ES2560447T3/en active Active
- 2005-07-14 ES ES15186588.8T patent/ES2667220T3/en active Active
- 2005-07-14 WO PCT/EP2005/007666 patent/WO2006015684A2/en active Application Filing
- 2005-07-14 EP EP15186588.8A patent/EP2987785B1/en not_active Not-in-force
- 2005-07-14 CN CN2005800265919A patent/CN101031542B/en not_active Expired - Fee Related
- 2005-07-14 EP EP05775924.3A patent/EP1778631B1/en not_active Not-in-force
- 2005-07-14 CA CA002573047A patent/CA2573047A1/en not_active Abandoned
- 2005-07-14 MX MX2007000345A patent/MX2007000345A/en active IP Right Grant
- 2005-07-14 JP JP2007524209A patent/JP4773441B2/en not_active Expired - Fee Related
- 2005-07-14 BR BRPI0513072-7A patent/BRPI0513072A/en not_active Application Discontinuation
- 2005-07-14 CN CN2010101447601A patent/CN101812004B/en not_active Expired - Fee Related
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ES2560447T3 (en) | 2016-02-19 |
CN101031542B (en) | 2010-05-12 |
JP5306402B2 (en) | 2013-10-02 |
US7119233B2 (en) | 2006-10-10 |
JP2011132256A (en) | 2011-07-07 |
CN101812004A (en) | 2010-08-25 |
JP2008508330A (en) | 2008-03-21 |
DE102004038053A1 (en) | 2006-04-27 |
MX2007000345A (en) | 2007-03-07 |
RU2383531C2 (en) | 2010-03-10 |
WO2006015684A2 (en) | 2006-02-16 |
RU2007108071A (en) | 2008-09-20 |
EP1778631B1 (en) | 2015-11-18 |
JP4773441B2 (en) | 2011-09-14 |
ES2667220T3 (en) | 2018-05-10 |
EP2987785A1 (en) | 2016-02-24 |
WO2006015684A3 (en) | 2006-08-03 |
CN101031542A (en) | 2007-09-05 |
US20060030739A1 (en) | 2006-02-09 |
EP2987785B1 (en) | 2018-03-14 |
BRPI0513072A (en) | 2008-04-22 |
EP1778631A2 (en) | 2007-05-02 |
CN101812004B (en) | 2012-09-19 |
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